EP1501146A2 - Système de pile à combustible, méthode pour le fonctionnement d'un pile à combustible, programme, et enregistreur - Google Patents

Système de pile à combustible, méthode pour le fonctionnement d'un pile à combustible, programme, et enregistreur Download PDF

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Publication number
EP1501146A2
EP1501146A2 EP04017146A EP04017146A EP1501146A2 EP 1501146 A2 EP1501146 A2 EP 1501146A2 EP 04017146 A EP04017146 A EP 04017146A EP 04017146 A EP04017146 A EP 04017146A EP 1501146 A2 EP1501146 A2 EP 1501146A2
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EP
European Patent Office
Prior art keywords
aforementioned
fuel cell
constant
resistance
predetermined
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04017146A
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German (de)
English (en)
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EP1501146A3 (fr
Inventor
Yasuo Takebe
Masatoshi Teranishi
Takashi Nakagawa
Makoto Uchida
Terutsugu Segawa
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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Publication of EP1501146A2 publication Critical patent/EP1501146A2/fr
Publication of EP1501146A3 publication Critical patent/EP1501146A3/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04305—Modeling, demonstration models of fuel cells, e.g. for training purposes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
    • H01M8/04225—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells during start-up
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
    • H01M8/04228—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells during shut-down
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/043—Processes for controlling fuel cells or fuel cell systems applied during specific periods
    • H01M8/04303—Processes for controlling fuel cells or fuel cell systems applied during specific periods applied during shut-down
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/367—Software therefor, e.g. for battery testing using modelling or look-up tables
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
    • G01R31/389—Measuring internal impedance, internal conductance or related variables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04223—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids during start-up or shut-down; Depolarisation or activation, e.g. purging; Means for short-circuiting defective fuel cells
    • H01M8/04231—Purging of the reactants
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a fuel cell system, fuel cell operation method, program, and recording medium for the prevention of such problems as power generation abnormality in a polymer electrolyte fuel cell.
  • fuel cell is to be understood as generic term if the context is not different if not the opposite is to be taken from the present specification.
  • fuel cell as generic term includes particularly arrangements in which a plurality of individual cells of fuel cell type cooperate, which is the case, for instance, in one fuel cell stack, a multiplicity of such stacks, fuel cell units or even fuel cell plants.
  • Fuel cells in the present specification in general are simply called “cells”.
  • the term “fuel cell stack” is used as well in the given context.
  • fuel cell the broader term “fuel cell power generation” or more simply “fuel cell system” is used (cf. reference number “1” in Fig. 1 of the drawings). Shorter one could use as well the term “fuel cell means”.
  • fuel “cell stack” sometimes is called simply “stacks” (reference signs 21, 22 ... 2n in Fig. 1 of the drawings) and the individual cells themselves have in Fig. 1 the reference number 31, 32, ... 3m. This wording is maintained in the description of the further embodiments.
  • a fuel cell generates power by supplying to the cathode an oxidizing agent containing oxygen and by supplying to the anode a fuel gas containing hydrogen, and it is composed of a fuel cell comprised of a cathode-anode pair or a fuel cell stack in which multiple fuel cells are connected in series.
  • a power generation abnormality in a fuel cell generally is detected by monitoring the fuel cell voltage.
  • this method is poor at determining the cause of the power generation abnormality. To be more specific, it cannot be determined whether a fuel cell voltage drop occurred because gas diffusion inhibition increased diffusion resistance or because decreased electrode reactivity increased reaction resistance.
  • One technique for determining the cause of such a power generation abnormality is as follows: The AC impedance in the normal state is measured in advance at a specific frequency, after which alternating current with this specific frequency is impressed also during power generation, and the impedance in the power generation state is measured. Then the AC impedance in the normal state and the impedance in the power generation state are compared (for example, refer to Unexamined Patent Application Publication No. 2002-367650 (Patent Document 1)).
  • impedance measurement devices 71, 72,...7n are provided in multiple stacks 21, 22,...2n (also called fuel cell stacks or PEFC stacks), respectively.
  • the AC voltages generated by impedance measurement devices 71, 72,...7n are impressed in multiple stacks 21, 22,...2n, after which the impedances are measured.
  • the AC voltage is impressed at least at the frequencies 5 Hz and 40 Hz, and the diffusion resistance and reaction resistance are determined from the impedances at these frequencies.
  • Inverter 6 ordinarily performs a switching operation, and its load impedance varies constantly. As a result, it is difficult to precisely determine the impedance of each stack 21, 22,...2n, by subtracting the impedance of inverter 6.
  • each cell 31, 32,...3m also called fuel cell or PEFC cell.
  • each cell forming stacks 21, 22,...2n is in a different state, so the impedance differs in each cell 31, 32,...3m.
  • the impedance of the entire stack combines the impedances of cells 31, 32,...3m, so it is almost impossible to derive the impedances of cells 31, 32,...3m from this value.
  • the problem has been the lack of an adequate response with high reliability, that is appropriate to the cause of the power generation abnormality in a fuel cell.
  • the present invention takes the aforementioned conventional problems into consideration, and it aims at providing a fuel cell system, fuel cell operation method, program, and recording medium that enable a more highly reliable response that is appropriate to the cause of the power generation abnormality of a fuel cell
  • An object of the invention is to overcome the above mentioned problems of the prior art with a more highly reliable response than before without undergoing the complications of monitoring each individual cell separately.
  • Claim 43 to claim 45 concern further realisations of the invention as method, program and recording medium of the program.
  • the present invention has the advantage of enabling a more highly reliable response that is appropriate to the cause of a power generation abnormality in a fuel cell.
  • the fuel cell power generation system of the present embodiment is a fuel cell power generation system that generates power by supplying an oxidizing agent containing oxygen to the cathode and by supplying a fuel gas containing hydrogen to the anode.
  • fuel cell power generation system of the present embodiment has AC signal generation block 503 that varies the load current of fuel cell 501 and voltage measurement block 504 that measures the voltage response of fuel cell 501.
  • Impedance measurement block 505 measures the impedance of fuel cell 501, from the phase difference between the voltage response and the load current. The operating conditions are varied in accordance with the impedance value.
  • load 502 which is equivalent to an orthogonal conversion inverter for converting DC to AC (ditto hereinafter), is connected in series with the fuel cell 501 to be measured.
  • the fuel cell power generation system of the present embodiment can easily and precisely measure the impedance in the fuel cell power generation system. Next, the operation of the fuel cell power generation system of the present embodiment will be explained. Furthermore, while the operation of the fuel cell power generation system of the present embodiment is being explained, one embodiment of the fuel cell operation method of the present invention also will be explained. (The same applies to the other embodiments.)
  • Fuel cell 501 is connected to load 502.
  • the current that flows through load 502 is controlled by the signal from AC signal generation block 503, and the load current varied at the AC signal frequency flows in fuel cell 501.
  • fuel cell control block 506 controls by varying the operating conditions for fuel cell 501, in accordance with the impedance value.
  • the representative fuel cell is composed of one fuel cell.
  • it after connecting a fuel cell stack composed of multiple stacked fuel cells, instead of a fuel cell, it also is possible to measure the impedance of the entire fuel cell stack.
  • the means that includes load 502 and AC signal generation block 503 corresponds to the load current variation means of the present invention.
  • Voltage measurement block 504 corresponds to the measurement means of the present invention.
  • Impedance measurement block 505 corresponds to the computation means of the present invention.
  • Fuel cell control block 506 corresponds to the fuel cell control means of the present invention.
  • the fuel cell power generation system of the present embodiment corresponds to the fuel cell system of the present invention. This completes the explanation of the configuration and operation of the fuel cell system of the present embodiment. Next, the principles of impedance computation and operating condition control in the same fuel cell system will be explained in detail.
  • the fuel cells that make up a fuel cell stack are composed of a hydrogen ion-conductive electrolyte membrane and electrodes disposed on both sides thereof (i.e., the so-called polymer electrolyte type).
  • a fuel cell is configured by providing a pair of separator plates having a gas flow channel that supplies and discharges fuel gas on one side of this electrode and having a gas flow channel that supplies and discharges oxygen-containing gas on the other side. Furthermore, the electrode that supplies fuel gas is the anode, and the electrode that supplies oxygen-containing gas is the cathode.
  • a fuel cell stack is formed by stacking several tens to several hundreds of this fuel cell.
  • the fuel cell impedance consists of the impedance of the anode, the impedance of the cathode, the electrolyte membrane's impedance, and contact resistance of each component.
  • the imaginary part is plotted against the real part of the impedance of a typical fuel cell, in Fig. 2, the diagram in which are plotted the impedances measured by sweeping the frequencies of Embodiment 1 of the present invention.
  • Fig. 3 is an diagram of the equivalent circuit representing the cell impedance of Embodiment 1 of the present invention, has very high precision.
  • An AC current which has frequency f and a small amplitude of at most 10% of the current amplitude of the DC current retrieved from the fuel cell, is retrieved after superimposing it on the DC current.
  • the load current variation range is 0-200% of the rated output of the fuel cell.
  • the impedance is computed from the amplitude and phase of the AC component of the cell current and from the AC component of the cell voltage, which are measured at that time.
  • Fig. 4 which shows the relationship between the S/N ratio and the ratio of the AC current amplitude to the DC current in Embodiment 1 of the present invention
  • the S/N ratio saturates when the ratio of the AC current amplitude to the DC current exceeds 5%, and even if the amplitude increases further, the S/N ratio hardly increases.
  • the current flowing through the cell is associated with the charge transfer resulting from the chemical reaction, so when the AC current amplitude is increased, the reaction volume relative to the supply gas volume (i.e., the gas utilization rate) varies.
  • the impressed AC current has an amplitude of at most 10% of the DC current, there is little variation in the gas utilization rate, and measurement is unaffected. However, if the impressed AC current has an amplitude exceeding 10% of the DC current, the effect of variation in the gas utilization rate is not negligible, and a measurement error occurs readily.
  • the amplitude of the impressed AC current preferably is about 5-10% of the DC current.
  • the complex impedance Z at that time can be computed from E and I measured after the retrieval of the AC current with frequency f.
  • frequency f of the AC current to be retrieved is swept from about 0.1 Hz to about 1000 Hz, and the complex impedance Z at each frequency is computed similarly.
  • Fig. 5 is a diagram of the Cole-Cole plot of Embodiment 1 of the present invention.
  • the Cole-Cole plot (as in Fig. 6) for the equivalent circuit having resistor (resistance) and capacitor (capacitance) sets (R 1 , C 1 ), (R 2 , C 2 ), and (R 3 , C 3 ) as well as the resistor (resistance) R 3 has a shape that superimposes and combines three semicircles.
  • the three semicircles are shown as solid lines, and the shape that combines these superimposed semicircles is shown as a dashed line.
  • the radii and center coordinates of the semicircles are determined one by one, from the low-frequency side, to conform to the drawn shapes.
  • the center coordinates are set to X 1 , X 2 , and X 3 , respectively, and the diameters are set to D 1 , D 2 , and D 3 , respectively.
  • Fig. 6 is a diagram in which are plotted the sets of components of the equivalent circuit, following measurements obtained after varying the air utilization rate of Embodiment 1 of the present invention.
  • broken line 401 connects (C 1 , R 1 ), (C 2 , R 2 ), and (C 3 , R 3 ) for the case of the 60% air utilization rate (i.e., oxygen utilization rate)
  • broken line 402 connects (C 1 , R 1 ), (C2, R2), and (C 3 , R 3 ) for the case of the 40% air utilization rate
  • broken line 403 connects (C 1 , R 1 ), (C 2 , R 2 ), and (C 3 , R 3 ) for the case of a 20% air utilization rate.
  • C 1 and R 1 are equivalent to the reactive impedance of the anode
  • C 2 and R 2 are equivalent to the reactive impedance of the cathode
  • C 3 and R 3 are equivalent to the diffusion impedance of the cathode.
  • the impedance of each fuel cell during normal operation is measured in advance, and the values of the components of the equivalent circuit during normal operation are stored.
  • Steps 1-3 After power generation starts, the impedance is measured as needed. The values of the components of the equivalent circuit are determined from the measured impedances.
  • Steps 4-8 Determined next is the area in which equivalent circuit set (C 3 , R 3 ) lies in Fig. 10, the diagram for showing the area of (C 3 , R 3 ) in the system control of Embodiment 1 of the present invention.
  • (C 3 , R 3 ) is the component based on the diffusion impedance of the cathode.
  • the initial value 901 of (C 3 , R 3 ) in Fig. 10 corresponds to the normal value of (C 3 , R 3 ). Furthermore, area 91 is the region defined by [Relationship 21] -0.00041C 3 + 0.015 ⁇ R 3 area 92 is the region defined by [Relationship 22] R 3 ⁇ -0.00041C 3 + 0.098 area 93 is the region defined by and area 94 is the region defined by
  • Steps 9-10 When R 3 decreases and (C 3 , R 3 ) enters area 92, it can be inferred that drying occurred, so, by increasing the air utilization ratio U o , drying is controlled and R 3 is increased.
  • Steps 11-12 Even after C 3 decreases and (C 3 , R 3 ) enters area 93, it still can be considered wetting progress, but it is believed to be attributable to decreased fuel cell temperature. Consequently, by decreasing the amount of cooling water to increase the fuel cell temperature, the wetting is eliminated and C 3 is increased.
  • Steps 13-14 Conversely, after C 3 increases and (C 3 , R 3 ) enters area 94, by increasing the amount of cooling water to reduce the cell temperature, drying is controlled and C 3 is decreased.
  • Fig. 11 is used to determine the area in which (C 2 , R 2 ) lies in Fig. 11, the diagram that shows the areas of (C 2 , R 2 ) in the system control of Embodiment 1 of the present invention.
  • (C 2 , R 2 ) is the component based on the reactive impedance of the cathode.
  • the initial value 1001 of (C 2 , R 2 ) in Fig. 11 corresponds to the normal value of (C 2 , R 2 ).
  • area 101 is the region defined by [Relationship 25] C 2 ⁇ 1000R 2 - 5
  • area 102 is the region defined by and area 103 is the region defined by
  • Steps 15-19 When C 2 decreases and (C 2 , R 2 ) enters area 101, it is believed that the reactivity of the cathode catalyst decreased and the apparent electrode surface area decreased, so a recovery operation is performed to increase C 2 .
  • the cathode voltage is decreased (i.e., the fuel cell voltage is decreased) either by flowing the load current after shutting off the air while flowing the fuel gas or by flowing, instead of air, a gas with an oxygen partial pressure lower than that of air, for example.
  • Such a recovery operation enables the restoration of a cathode catalyst with reactivity decreased by the adhesion of contaminants or the progress of oxidation.
  • Steps 20-21 When R 2 increases and (C 2 , R 2 ) enters area 102, it can be inferred that the catalyst dried and the reactivity decreased, so air humidification is increased to decrease R 2 .
  • Steps 22-23 Conversely, when R 2 decreases and (C 2 , R 2 ) enters area 103, it is possible to determine that catalyst wetting is excessive, so air humidification is decreased to increase R 2 .
  • Fig. 12 is used to determine the area in which (C 1 , R 1 ) lies in Fig. 12, the diagram that shows the areas of (C 1 , R 1 ) in the system control of Embodiment 1 of the present invention.
  • (C 1 , R 1 ) is the component based on the reactive impedance of the anode.
  • the initial value 1101 of (C 1 , R 1 ) in Fig. 12 corresponds to the normal value of (C 1 , R 1 ).
  • area 111 is the region defined by [Relationship 28] C 1 ⁇ 625R 1 - 0.75
  • area 112 is the region defined by area 113 is the region defined by and area 114 is the region defined by [Relationship 31] 625R 1 + 1.1 ⁇ C 1
  • Steps 24-28 When C 1 decreases and (C 1 , R 1 ) enters area 111, it is believed that the anode catalyst was poisoned and reactivity decreased, and that the apparent electrode surface area decreased, so the amount of air bleeding is increased in an attempt to increase C 1 .
  • Air bleeding adds a small amount of air to the fuel gas and, on the catalyst surface, oxidizes and eliminates the carbon monoxide that poisons the catalyst.
  • Steps 29-30 When R 1 increases and (C 1 , R 1 ) lies in area 112, it can be inferred that the anode catalyst dried as the result of excessive fuel gas, so the fuel utilization rate U f is decreased and operation is performed to decrease R 1 .
  • Steps 31-32 Conversely, when R 1 decreases and (C 1 , R 1 ) lies in area 113, the fuel utilization rate U f is increased to increase R 1 .
  • Steps 33-34 When C 1 increases and (C 1 , R 1 ) lies in area 114, it is possible to determine that the amount of air bleeding is excessive, so the amount of air bleeding is decreased to decrease C 1 .
  • step 2 the flow returns to the impedance measurement (i.e., step 2) of Fig. 7, and the same operations are repeated.
  • the configuration of the fuel cell power generation system of the present embodiment will be explained with reference mainly to Fig. 13, the block diagram of the fuel cell power generation system of Embodiment 2 of the present invention.
  • the configuration of the fuel cell power generation system in the present embodiment resembles the configuration of the fuel cell power generation system in aforementioned Embodiment 1, so the following description will concern mainly the differences between the two. (This also applies to Embodiment 3.)
  • the fuel cell power generation system of the present embodiment is a fuel cell power generation system that generates power by supplying an oxidizing agent containing oxygen to the cathode, and by supplying a fuel gas containing hydrogen to the anode.
  • the fuel cell power generation system of the present embodiment has a load control block 603 that varies stepwise the load current of fuel cell 601 and has a voltage measurement block 604 that measures the transient voltage response of fuel cell 601.
  • the system digitizes and subjects to Fourier transformation the time from load current variation and the voltage at that time.
  • impedance measurement block 606 measures the impedance of fuel cell 601, and the operating conditions are varied in accordance with the impedance.
  • the fuel cell power generation system of the present embodiment can rapidly measure the impedance at all frequencies.
  • Fuel cell 601 is connected to load 602, and load 602 is controlled by load control block 603.
  • the stepped load current flows in fuel cell 601.
  • the load current variation range is set to 0-200% of the rated output of the fuel cell, and the stepped current variation is set to at least 10%.
  • Voltage measurement block 604 monitors changes in the voltage of the fuel cell during load current variation. The time from load variation and the voltage at that time are digitized, after which, as described hereinafter, Fourier transform block 605 subjects them to Fourier transformation.
  • impedance measurement block 606 computes the impedance, after which fuel cell control block 607 controls to vary the operating conditions of fuel cell 601.
  • the load current may be varied intentionally for impedance measurement. However, this may be combined with varying the load current when switching the system ON/OFF or when increasing/decreasing the power generation capacity.
  • Fourier transform block 605 computes frequency functions FI step (f) and FE step (f) from time functions I step (t) and E step (t).
  • Fourier transform block 605 is composed of a digital computer, etc., so by dividing time functions I step (t) and E step (t) into a finite number and digitally computing, a finite number of FI step (f) and FE step (f) are determined, after which a finite number of impedances Z step (f) are computed.
  • the means that includes load 602 and load control block 603 corresponds to the load current variation means of the present invention
  • voltage measurement block 604 corresponds to the measurement means of the present invention
  • impedance measurement block 606 corresponds to the computation means of the present invention
  • fuel cell control block 607 corresponds to the fuel cell control means of the present invention
  • the fuel cell power generation system of the present embodiment corresponds to the fuel cell system of the present invention.
  • the fuel cell power generation system of the present embodiment is a system having fuel cell stack 702, in which are connected in series multiple fuel cells 701 that generate power by supplying to the cathode an oxidizing agent containing oxygen, and by supplying to the anode a fuel gas containing hydrogen.
  • the fuel cell power generation system of the present embodiment is a system having load control block 704 that varies the load 703 common to each fuel cell 701 and voltage measurement block 705 that can measure the voltage of each fuel cell 701.
  • Impedance measurement block 707 measures the impedance of each fuel cell 701, and the operating conditions are varied in accordance with the impedance.
  • the fuel cell power generation system of the present embodiment can measure the impedance of each fuel cell 701 making up fuel cell stack 702.
  • Fuel cell stack 702 which is composed of stacked fuel cells 701, is connected to load 703. Load 703 is controlled by load control block 704, and a stepped load current flows in fuel cell stack 702.
  • the electrodes of each fuel cell 701 are connected to voltage measurement block 705.
  • Voltage measurement block 705 monitors changes in the voltage of each fuel cell 701 during load current variation. It digitizes the time from load variation and the voltage at that time, which are subjected to Fourier transformation by Fourier transform block 706.
  • impedance measurement block 707 computes the impedance. Then fuel cell control block 708 controls to vary the operating conditions of each fuel cell 701, in accordance with the impedance.
  • the load current may be varied intentionally for impedance measurement. However, this may be combined with varying the load current when switching the system ON/OFF or when increasing/decreasing the power generation capacity.
  • the means that includes load 703 and load control block 704 corresponds to the load current variation means of the present invention
  • voltage measurement block 705 corresponds to the measurement means of the present invention
  • impedance measurement block 707 corresponds to the computation means of the present invention
  • fuel cell control block 708 corresponds to the fuel cell control means of the present invention
  • the fuel cell power generation system of the present embodiment corresponds to the fuel cell system of the present invention.
  • Fuel cell stack 802 which is composed of stacked fuel cells 801, is connected to inverter 803 and is connected to an external load.
  • Each fuel cell 801 is equipped with an automatic connection device 44, and connection device control line 45, voltage measurement line 46, and current line 47 are connected via the terminals of automatic connection device 44.
  • connection device control block 804 The terminal of automatic connection device 44 is opened during normal operation, and address signals from connection device control block 804 are received via connection device control line 45. Only if the address signal matches the address of automatic connection device 44 are voltage measurement line 46 and current line 47 connected, via automatic connection device 44, to fuel cell 801.
  • Voltage measurement block 809 monitors a fuel cell 801 during load current variation.
  • Impedance measurement block 806 computes the impedance from its voltage response, and fuel cell control block 805 controls to vary the operating conditions of fuel cell 801, in accordance with the impedance.
  • the impedance of each cell during normal operation is measured in advance, and both the address of the automatic connection device housed in each cell and the equivalent circuit component values discussed hereinafter are stored in advance.
  • the fuel cell system of the present embodiment determines the cause of an abnormality and responds appropriately to the cause of the abnormality, by using automatic connection device 44 housed in each cell to send specific address control signals to each cell, to connect only the target cell with the matching address to impedance measurement block 806.
  • Automatic connection device 44 has a different address for each cell. It receives specific signals from connection device control block 804, and only if the address and specific signal match is a connection made with impedance measurement block 806, electronic load block 807, AC signal generation block 808 or voltage measurement block 809.
  • automatic connection device 44 disconnects from impedance measurement block 806, electronic load block 807, AC signal generation block 808 or voltage measurement block 809.
  • the means including electronic load block 807 and AC signal generation block 808 corresponds to the load current variation means of the present invention
  • voltage measurement block 809 corresponds to the measurement means of the present invention
  • impedance measurement block 806 corresponds to the computation means of the present invention
  • fuel cell control block 805 corresponds to the fuel cell control means of the present invention
  • the fuel cell power generation system of the present embodiment corresponds to the fuel cell system of the present invention.
  • current line 47 corresponds to the first wiring of the present invention
  • voltage measurement line 46 corresponds to the second wiring of the present invention
  • automatic connection device 44 corresponds to the connection means of the present invention
  • the means including connection device control block 804 and connection device control line 45 corresponds to the connection means control means of the present invention.
  • the impedance of a cell is composed of the anode impedance, the cathode impedance, and the electrolyte membrane impedance and contact resistance.
  • Frequency f' of the AC current to be retrieved is swept from about 0.1 Hz to about 1000 Hz, and the complex impedance Z' at each frequency is computed. Furthermore, it is preferable to measure the impedance while varying multiple specific frequencies and to measure the impedance by using an alternating current in which multiple specific frequencies are admixed.
  • the Cole-Cole plot for the equivalent circuit having set (R 1 ', C 1 ') containing a resistor (resistance) and capacitor (capacitance), set (R 2 ', C 2 ', W 2 ') containing a resistor (resistance), capacitor (capacitance), and Warburg resistor (Warburg resistance), and resistor (resistance) R 3 ' becomes the shape formed by superimposing and combining the curve connecting the circular arc and straight line and the two semicircles (i.e., the curve corresponding to the Cole-Cole plot for a Warburg resistor).
  • the center coordinates and radii of the circular arcs are determined one by one, from the low-frequency side.
  • the center coordinate is set to X 1 ' and X 2 ', respectively, and the diameter is set to D 1 ' and D 2 ', respectively.
  • the width is set to D 3 '.
  • W 2T ' is the constant that becomes the gas diffusibility index.
  • C 1 ' and R 1 ' vary.
  • C 2 ' and R 2 ' vary.
  • W 2R ' varies. From this, it was determined that C 1 ' corresponds to the electric double-layer capacity of the anode; R 1 ' corresponds to the reaction resistance of the anode; C 2 ' corresponds to the electric double-layer capacity of the cathode; R 2 ' corresponds to the reaction resistance of the cathode; and W 2R ' corresponds to the diffusion resistance of the cathode.
  • R 3 ' decreases when the humidification is increased, it is known that R 3 ' corresponds to the resistance of the polymer membrane.
  • abnormality and deterioration of the reaction resistance of the anode catalyst layer can be detected and understood by investigating changes in R 1 '.
  • abnormality and deterioration of the reactive area of the cathode catalyst layer can be detected and understood by investigating changes in C 2 '.
  • abnormality and deterioration of the reaction resistance of the cathode catalyst layer can be detected and understood by investigating changes in R 2 '.
  • abnormality and deterioration of the diffusion resistance of the cathode gas diffusion layer can be detected and understood by investigating changes in W 2R '.
  • abnormality and deterioration of the humidification state of the polymer membrane can be detected and understood by investigating changes in R 3 '.
  • Fig. 19 which is part 1 of the flowchart for explaining the system control of Embodiment 4 of the present invention
  • Fig. 20 which is part 2 of the flowchart for explaining the system control of Embodiment 4 of the present invention
  • Fig. 21 which is part 3 of the flowchart for explaining the system control of Embodiment 4 of the present invention.
  • Steps 1-3 After power generation starts, the impedance is measured as needed. Of course, fuel cells may be measured in address order or in random order. The values of the components of the equivalent circuit are determined from the measured impedances.
  • W 2 ' is the component based on the cathode gas diffusion
  • W 2R ' represents the magnitude of the diffusion resistance
  • Steps 4-10 It can be concluded that, when W 2R ' increases, the gas diffusibility decreases as the result of the wetting progress. Therefore, when the value of W 2R ' exceeds the predetermined value, the air utilization rate U o ' is decreased for a given amount of time, and the gas flow rate is increased, thereby eliminating the wetting. The number of iterations of the operation that decreases the air utilization rate U o ' for a given amount of time is counted.
  • the wetting is eliminated by increasing the cell temperature and decreasing the cooling water volume for a given amount of time.
  • the number of iterations of the operation that decreases the cooling water volume for a given amount of time is counted.
  • the alarm can be used to notify the user of the abnormality, to suggest maintenance, and to identify the cause of the problem during maintenance.
  • Steps 11-12 In the state where W 2R ' is below the predetermined value, it is inferred that drying progressed, so it is possible to prevent drying by increasing U o '. (The gas flow rate also may be decreased.)
  • R 3 ' is determined.
  • R 3 ' represents the magnitude of the resistance of the polymer membrane. Steps 13-14: When R 3 ' increases, it can be inferred the that polymer membrane resistance increased as the result of drying, so drying can be prevented by increasing the cooling water volume, thereby creating a state that facilitates wetting. In Fig. 20, R 2 ' and C 2 ' are determined.
  • R 2 ' represents the reaction resistance of the catalyst layer of the cathode
  • C 2 ' represents the reactive area of the catalyst layer of the cathode.
  • Steps 15-19 When C 2 ' decreases, it is believed that the reactivity of the electrode catalyst decreased, so the apparent electrode surface area decreased. Therefore, when C 2 ' is less than the predetermined value, the recovery operation is performed.
  • Steps 20-21 When R 2 ' increases, it can be inferred that the catalyst dried so the reactivity decreased. Therefore, when R 2 ' exceeds the predetermined value, the air humidification is increased.
  • Steps 22-23 Conversely, when R 2 ' decreases, catalyst wetting is excessive, so when R 2 ' is less than the specified value, air humidification is decreased.
  • Fig. 21 is used to determine R 1 ' and C 1 '.
  • R 1 ' represents the reaction resistance of the anode catalyst layer
  • C 1 ' represents the reactive area of the anode catalyst layer.
  • Steps 24-28 When C 1 ' decreases, it is believed that the anode catalyst was poisoned and the reactivity decreased, so the apparent electrode surface area decreased. So, the amount of air bleeding is increased when C 1 ' is less than the predetermined value. Air bleeding adds a small amount of air to the fuel gas and, on the catalyst surface, oxidizes and eliminates the carbon monoxide that poisons the catalyst.
  • C 1 ' is less than the predetermined value even after the amount of air bleeding is increased, it implies considerable deterioration of the anode catalyst, so an alarm is output and operation is stopped.
  • Steps 29-30 When R 1 ' increases, it can be inferred that the anode catalyst dried as the result of excessive fuel gas, so when R 1 ' exceeds the predetermined value, the fuel utilization rate U f is decreased and operation is performed. (Furthermore, fuel gas humidification also may be increased.)
  • Steps 31-32 Conversely, when R 1 ' decreases, excessive catalyst wetting can be inferred. So when R 1 ' is less than the predetermined value, the fuel utilization rate U f is increased and operation is performed. (Furthermore, fuel gas humidification also may be decreased.)
  • Steps 33-34 When C 1 ' increases, excessive air bleeding can be inferred. So when C 1 ' exceeds the predetermined value, the amount of air bleeding is decreased. Furthermore, the various predetermined values mentioned previously are set appropriately, within the range that allows the normal operating state to be maintained under system control.
  • connection device control block 804. The same flow is used to measure and control the impedance of the target cell for which the address signal and the address of automatic connection device 44 agree.
  • the address signal changes, thereby enabling the successive measurement of all fuel cells in fuel cell stack 802.
  • the gas diffusion layer was produced by means of the following method. Then carbon paper (TGPH-060, made by Toray Industries, Inc.) was impregnated with 10 wt% (dry weight) polytetrafluoroethylene suspension (Lubron LDW-40, made by Daikin Industries, Ltd.), after which water-repelling treatment was performed using a hot-air dryer to heating at 350 °C.
  • carbon paper TGPH-060, made by Toray Industries, Inc.
  • 10 wt% (dry weight) polytetrafluoroethylene suspension Libron LDW-40, made by Daikin Industries, Ltd.
  • the suspension was produced by mixing 30 wt% (dry weight) polytetrafluoroethylene suspension (Lubron LDW-40, made by Daikin Industries, Ltd.) as the fluoropolymer, into Denka Black (made by Denki Kagaku Kogyo K.K.) as the carbon powder.
  • the suspension produced in this manner was coated onto the carbon paper that was subjected to the water-repellent treatment mentioned previously, and a gas diffusion layer containing a conductive layer containing a polymer was produced by using a hot-air dryer to heat at 350 °C.
  • the membrane-electrode assembly (MEA) was produced by means of the following method.
  • Catalyst paste was prepared by adding 10 g of water to 10 g of material (TEC10E50E, made by Tanaka Kikinzoku Kogyo K.K.) supporting 50-wt% platinum particles (average particle diameter: 30 ⁇ ) on electroconductive carbon powder, and by then admixing 55 g of 9-wt% ethanol solution of hydrogen ion-conductive polymer electrolyte (Flemion, made by Asahi Glass Co.).
  • the fuel electrode-side catalyst layer was formed by drying this paste after applying it to polypropylene film by means of bar-coating with a wire bar, thereby forming the oxidizing agent electrode-side catalyst layer and cathode-side catalyst layer, respectively.
  • the amount of catalyst layer applied was controlled at a platinum content 0.3 mg per cm 2 .
  • Catalyst paste was prepared by adding 10 g of water to 10 g of material (TEC61E54, made by Tanaka Kikinzoku Kogyo K.K.) supporting a platinum-ruthenium alloy on electroconductive carbon powder, and by then admixing 50 g of 9% ethanol solution of hydrogen ion-conductive polymer electrolyte membrane (Flemion, made by Asahi Glass Co.).
  • the fuel electrode-side catalyst layer was formed by drying this paste after applying it to polypropylene film by means of bar-coating with a wire bar, thereby forming the fuel electrode-side catalyst layer and anode-side catalyst layer, respectively.
  • the amount of catalyst layer applied was controlled at a platinum content 0.3 mg per cm 2 .
  • Polypropylene film with this catalyst layer was cut into 6-cm-square pieces, and the hydrogen ion-conductive polymer electrolyte membrane (GoreSelect, made by Japan Goretex, Inc.; membrane thickness: 30 ⁇ m) was interposed between two sheets of the aforementioned polypropylene film with a catalyst layer, with the catalyst layers inside.
  • the polymer electrolyte membrane interposed between two sheets of polypropylene film in this manner was hot-pressed for 10 min. at 130 °C, after which the polypropylene film was eliminated, thereby yielding a polymer electrolyte membrane with catalyst layers.
  • An MEA was formed by interposing this polymer electrolyte membrane with catalyst layers between gas diffusion layers, with their polymer-containing electroconductive layers on the inside.
  • separator plates were formed by cutting a gas flow channel and a cooling water flow channel into graphite plates.
  • the MEA was interposed between a pair of separator plates, thereby forming a fuel cell.
  • This fuel cell was used to produce the fuel cell power generation system with the composition of Embodiment 1.
  • mixed gas hydrogen: 80%; carbon dioxide: 20%; carbon monoxide: 20 ppm
  • Power was generated at an 80% fuel utilization rate, a 40% oxygen utilization rate, and a 200-mA/cm 2 current density.
  • the cooling water was regulated to 70 °C on the inlet side and to 72-75 °C on the outlet side of fuel cell 501.
  • the voltage of fuel cell 501 was 0.75 V.
  • AC signals (1 Hz, 2 Hz, 4 Hz, 8 Hz, 16 Hz, 32 Hz, 64 Hz, 128 Hz, 256 Hz) were generated by AC signal generator block 503, and the load current was controlled in sync with these signals.
  • the load current was formed by superimposing the ⁇ 10-mA/cm 2 sine wave on the 200-mA/cm 2 direct current.
  • Voltage measurement block 504 monitored the voltage variation at this time; impedance measurement block 505 determined the impedance; and control was performed in accordance with the flow of Figs. 7-9.
  • Fig. 22 shows the variation over time in cell voltage in the comparative example and Example 1 of the present invention, as cell voltage 151 of Example 1.
  • cell voltage 151 was maintained at 0.70 V or higher.
  • a fuel cell was formed as in Example 1, and this fuel cell was used to produce a fuel cell power generation system with the configuration of Embodiment 1, as in Example 1.
  • Example 2 however, the U f values of step 30 and step 32 in Fig. 9 were not increased or decreased.
  • Fig. 23 shows the variation over time in cell voltage in Examples 2-6 of the present invention, as cell voltage 161 of Example 2.
  • cell voltage 161 was maintained at 0.70 V or higher.
  • a fuel cell was formed as in Example 1, and this fuel cell was used to produce a fuel cell power generation system with the configuration of Embodiment 1, as in Example 1.
  • Example 3 however, the air bleed amounts of step 25 and step 34 in Fig. 9 were not increased or decreased.
  • cell voltage 162 was maintained at 0.70 V or higher.
  • a fuel cell was formed as in Example 1, and this fuel cell was used to produce a fuel cell power generation system with the configuration of Embodiment 1, as in Example 1.
  • Example 4 however, the air humidification amounts of step 21 and step 23 in Fig. 8 were not increased or decreased.
  • cell voltage 163 was maintained at 0.70 V or higher.
  • a fuel cell was formed as in Example 1, and this fuel cell was used to produce a fuel cell power generation system with the configuration of Embodiment 1, as in Example 1.
  • Example 5 however, the cooling water volumes of step 12 and step 14 in Fig. 7 were not increased or decreased.
  • cell voltage 164 was maintained at 0.70 V or higher.
  • a fuel cell was formed as in Example 1, and this fuel cell was used to produce a fuel cell power generation system with the configuration of Embodiment 1, as in Example 1.
  • Example 6 however, the U o values of step 5, step 8, and step 10 in Fig. 7 were not increased or decreased.
  • cell voltage 165 was maintained at 0.70 V or higher.
  • a fuel cell was formed as in Example 1, and this fuel cell was used to produce a fuel cell power generation system with the configuration of Embodiment 2.
  • power was generated at an 80% fuel utilization rate, a 40% oxygen utilization rate, and the 200-mA/cm 2 rated current density, by supplying, on the fuel electrode side, hydrogen gas humidified to a dew point of 70 °C; and by supplying, on the oxygen electrode side, air humidified to a dew point of 70 °C.
  • Power was generated at an 80% fuel utilization rate, a 40% oxygen utilization rate, and a 200-mA/cm 2 current density.
  • the cooling water was regulated to 70 °C on the inlet side and to 72-75 °C on the outlet side of fuel cell 601.
  • the current density was decreased to 100 mA/cm 2 for 2 hours. Then, to cool fuel cell 601, the current density was set to zero and the system was stopped.
  • a control signal was sent from load control block 603, and the load current of load 602 was increased or decreased stepwise.
  • Voltage measurement block 604 monitored the voltage variation when the load increased or decreased, and these were digitized and subjected to Fourier transforms by Fourier transform block 605.
  • Impedance measurement block 606 determined the impedance, and control was performed in accordance with the flow of Figs. 7-9.
  • Example 1 Even 5000 hours after the start of operation, the cell voltage was maintained at 0.70 V or higher.
  • a fuel cell was formed as in Example 1, and 60 such fuel cells were stacked to form a fuel cell stack.
  • a lead wire was pulled from the separator plate of each fuel cell 701 and connected to voltage measurement block 705.
  • Power was generated at an 80% fuel utilization rate, a 40% oxygen utilization rate, and the 200-mA/cm 2 rated current density, by supplying, on the fuel electrode side, hydrogen gas humidified to a dew point of 70 °C, and by supplying, on the oxygen electrode side, air humidified to a dew point of 70 °C.
  • the cooling water was regulated to 70 °C on the inlet side and to 72-75 °C on the outlet side of fuel cell stack 702.
  • Example 7 operation was performed after increasing or decreasing the current density, the impedance at that time was measured, and control was performed in accordance with the flow of Figs. 7-9.
  • Example 1 Even 5000 hours after the start of operation, the cell voltage was maintained at 0.70 V or higher.
  • the fuel cell power generation system of the present comparative example was produced as a fuel cell power generation system with a configuration resembling that of Example 1.
  • Example 1 power was generated at an 80% fuel utilization rate, a 40% oxygen utilization rate, and a 200-mA/cm 2 current density, by supplying, on the fuel electrode side, hydrogen gas humidified to a dew point of 70 °C, and by supplying, on the oxygen electrode side, air humidified to a dew point of 70 °C.
  • the fuel cell power generation system of the present comparative example was operated without varying the load current and without measuring the impedance.
  • the change over time in cell voltage is shown in Fig. 22 as cell voltage 152 of the comparative example.
  • the program of the present invention is used to execute on a computer all or some of the steps of the fuel cell operation method of the present invention, and the program operates in cooperation with the computer.
  • the recording medium of the present invention supports the program used to execute on a computer all or some of the operations of all or some of the steps of the aforementioned fuel cell operation method of the present invention, and the recording medium is readable by computer and the aforementioned read program executes the aforementioned operations in cooperation with the aforementioned computer.
  • one usage mode of the program of the present invention may be the mode in which the program is recorded on a computer-readable recording medium, and operation is in cooperation with the computer.
  • one usage mode of the program of the present invention may be the mode in which the program is transmitted via a transmission medium, read by the computer, and operated in cooperation with the computer.
  • the recording medium includes a ROM, etc.
  • the transmission medium includes such transmission media as the Internet as well as light, radio waves, sound waves, etc.
  • the aforementioned computer of the present invention is not limited to simple hardware (e.g., the CPU), and it may include the firmware and the operating system as well as peripherals.
  • the configuration of the present invention may be implemented in software or it may be implemented in hardware.
  • the fuel cell system, fuel cell operation method, program, and recording medium of the present invention are useful because they allow fuel cell power generation abnormalities to be handled with higher reliability, as appropriate to the cause.

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EP04017146A 2003-07-24 2004-07-20 Système de pile à combustible, méthode pour le fonctionnement d'un pile à combustible, programme, et enregistreur Withdrawn EP1501146A3 (fr)

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